Mineral oil composition



Juy 26 l949 E. w. FULLER x-:rAL 2,476,972

MINERAL OIL COMPSTION Filed Nov. l5, 1946 2 Sheets-Sheet l OJO 0.07 Pff?CEA/7' BY W15/@HT UFA/5ML /A/ 0/1.

July 26, 1949- E. w. FULLER r-:TAL 2,475,972

MINERAL oIL COMPOSITION Filed Nov. 15, 1946 2 Sheets-Sheet 2 EVE'FETMFUALE/P oom ow- OQ O om. O9 O Ow QQ Dm Q o# INVENTO RS Patented July26, 1949 MINERAL OIL COMPOSITION Everett W. Fuller and Ellwood M. Johnlon, Woodbury. N. J., assignors to Socony-Vacnnm Oil Company,Incorporated, a corporation of New York Application November 15, 1946,Serial No. ,709,930

10 Claims. (Cl. 252-33A) This invention relates to a novel mineral oilcomposition and, more particularly, is concerned with a mineral oilcomposition containing minor proportions of an oil-soluble detergent andof an oil-soluble, phosphorusand sulfur-containing reaction product.

As is well known to those familiar with the art, mineral oils generallypossess one or more undesirable characteristics which limit their use.One such characteristic ls their instability under operating conditionsnormally encountered in present day engines, such that within arelatively short time, metal engine parts become contaminated withsludge. lacquer and resinous materials. In most instances, thesecontaminants are deposited on and about piston rings causing them tostick, the phenomenon being referred to in the art as ring-sticking." Asa. consequence of this instability of the mineral oils, engine operatingefliciency is seriously reduced. Another undesirable characteristic ofmineral oils is their tendency to oxidize producing acidic materials.These acidic materials corrode metal engine parts, particularly alloybearings such as those of the cadmium-silver, copper-lead, etc., type.As is also well known to those familiar with the art, numerous materialshave been proposed for use in mineral oils to counteract or retard theaforementioned undesirable characteristics. For example, the use ofoil-soluble metal sulfonates as addition agents for mineral oils hasbeen suggested, and they have been, found to be satisfactory from thestandpoint of imparting detergent properties to mineral oils.Unfortunately, however, such oil-soluble sulfonates fail to improve, andin some cases even impair, other characteristics of mineral oils. Insome instances, for example, oil-soluble metal sulfonates have increasedthe formation of acidic materials in mineral oils during use, thusinducing corrosion of metal parts with which the mineral oils come inContact.

As set forth in copending application Serial Number 539,597, led June 9,1944, now U. S. Patent No. 2,416,281, issued February 25, 1947, it hasbeen found that the corrosion and oxidation characteristics of'a mineraloil containing a small amount of an oil-soluble metal sulfonate can begreatly improved by incorporating therein a small amount of anoil-soluble, phosphorusand sulfur-containing reaction product of adicyclic terpene and a phosphorus sulde. More specically, it has beenfound that an extremely stable mineral oil having outstanding detergent,oxidation and corrosion characteristics can be obtained byincorporatingln a mineral oil containing a metal sulfonate, a smallamount of a reaction product of the aforesaid type. The oilsoluble metalsalts of wax-substituted aromatic sulfonic acids are mentionedspecifically in the copending application referred to and of these. thesodium, calcium, barium, zinc and aluminum salts are stated to bepreferred.

We have discovered that the oil-soluble magnesium sulfonates, when usedin combination with an oil-soluble phosphorusand sulfur-containingreaction product of a dicyclic terpene and a phosphorus sulfide, areparticularly effective in improving the corrosion and oxidationcharacteristics of mineral oils.

We have now found that mineral oils containing an oil-soluble magnesiumsulfonate and an oil-soluble phosphorusand sulfur-containing reactionproduct of a dicyclic terpene and a phosphorus sulde are extremelystable and possess outstanding detergent, oxidation and corrosioncharacteristics, and that oil-soluble magnesium sulfonates areappreciably more eifective in this connection, than other oil-solublemetal sulfonates both from the standpoint of weight per v cent of metal,and from the standpoint of mole per cent of metal which must be presentin the mineral oil in order to effect the desired improvements in thecharacteristics thereof. Indeed, due to their relatively low molecularweight. the use of magnesium salts has the inherent added advantage ofintroducing relatively small amounts of metal in mineral oils whichmeans low ash contents when the oil is burned.

Accordingly, it is an object of the present invention to provide animproved mineral oil composition. Another object is to provide a mineraloil composition possessing improved detergent, oxidation and corrosioncharacteristics. An important object is to afford a mineral oilconcentrate containing a mineral4 oil in combination with an oil-solublemagnesium sulfonate and an oil-soluble phosphorusand sulfur-containingreaction product of a phosphorus sulde with a dicyclic terpene. A morespecific object is to provide a mineral oil composition having improvedvcharacteristics which comprises in combination,

' minor proportions of an Oil-soluble magnesium conjunction with thefollowing drawings, in which:

Figure 1 shows a series of curves representing graphically therelationship between they E. C. (engine cleanliness) rating of variousoil blends containing anoil, 0.75% by weight of a pinenephosphoruspentasulde reaction product, and varying amounts of yvarious metal diwaxphenyl sulfonates, and the weight per cent of metal in the oil blends;and

Figure 2 shows a series of curves representing graphically therelationship between the E. C. rating of various oil blends containingan oil, 0.75% by weight of 'a pinene-phosphorus pentasulde reactionproduct and varying amounts of various metal diwax phenyl sulfonates,and the mole per cent of metal in the oil blends.

Broadly stated. the present invention provides a mineral oil compositioncomprising a. viscous mineral oil fraction having in admixturetherewith: an'oil-soluble magnesium sulfonate, and an oil-soluble,phosphorusand sulfur-containing reaction product obtained by reactionbetween I a phosphorus sulfide and a dicyclic terpene.

All oil-soluble magnesium sulfonates are contemplated herein. Typical ofoil-soluble magnesium sulfonates are those obtained from aromatichydrocarbons or substituted aromatic hydrocarbons, and a sulfonatingagent such as strong sulfuric' acid, oleum, chlorsulfonic acid and thelike. Other typical sulfonates are those obtained by treatment ofparains, naphthenes and various petroleum fractions-paranic, naphthenicor aromatic-with the same reagents. Preferred, however. are themagnesium salts of sulfonic acids of wax-substituted benzene and ynaphthalene, wherein the wax substitutent is a long-chain aliphatichydrocarbon group containing at least about eighteen carbon atoms and isobtained from paraflin wax. Especially preferred are the basic magnesiumsalts of diwax-benzene sulfonate.

The following examples illustrate these oilsoluble magnesium sulfonatesand the preparation thereof:

EXAMPLE 1 Preparation of the basic magnesium salt of diwax-phenylsulfonic acid A paraiiin wax having an average of 24 carbon atoms permolecule and a. melting point of 126 F. was chlorinated ata temperatureof about 100 C. with chlorine gas until the Weight of the wax hadincreased about 12%. The chlorowax thus obtained was then blown withnitrogen to remove any occluded chlorine and hydrogen chloride.

1000 grams of the chlorowax were then mixed with 500 grams of benzene ina 3-necked flask equipped with a stirrer, a reflux condenser and athermometer. The mixture was heated to a temperature of 60 C. Aluminumchloride'was then added slowly over a period of two hours. The additionof aluminum chloride was accompanied by a vigorous evolution of hydrogenchloride. The temperature was then raised to a tem- Derature of 80 C.and held there for one hour. The excess benzene was then removed byinverting the reflux condenser and heating to a temperature of 116 C.200 milliliters of benzene were thus recovered. The mixture was cooledto a temperature of 60 C. and then another 1000- grams of chlorowax wereadded slowly. [After completing the addition of this chlorowax, the

4 temperature was raised to 100 C. and held ther for one hour. Theproduct was allowed to stand overnight at a temperature of about C., andthen was separated from the sludge by decantation and iiltration bysuction through clay.

1738 gramsof lthe diwax-benzene thus obtained were placed in a 3-neckedask equipped with a stirrer and a thermometer and heated to atemperature of 40 C. 869 grams of oleum (15% S03) were added slowly tothe diwax-benzene from a dropping funnel at a rate regulated to maintainthetemperature below 50 C. The addition of oleum consumed about 3 hours.The mixture was then stirred for an additional hour to ensure completereaction. The mixture was then poured into 1000 milliliters of water andsubsequently, 1810 grams ofl mineral oil were added to the mixture. Themixture thus obtained was stirred thoroughly and then allowed to standuntil the water separated into a layer. The water layer was then drainedoff. The product thus obtained was approximately a 50% blend ofdiWax-benzene sulfonic acid in mineral oil and had a neutralizationnumber of 40.7.

. 500 grams of the diwax-phenyl sulfonic acidthus obtained were mixedwith 23.3 grams of magnesium hydroxide in a 3-necked flask equipped witha stirrer, a thermometer and water takeoff, and heated to a temperatureof 150 C, until all the water was distilled off. 'I'he mixture (oilblend) was then ltered through clay to yield a product weighing 359grams. This product contained 1,29% magnesium and 2.09% sulfur,indicating it to be principally the basic magnesium salt.

EXAMPLE 2 Preparation of the neutral magnesium salt of diwax-phenylsulfonic acid 2500 grams of the diwax-phenyl sulfonic acid produced inaccordance with the procedure set forth in Example 1 were mixed with amethanol solution of sodium hydroxide consisting of 75.7

- grams of sodium hydroxide in 550 milliliters of methanol, and themixture was heated to a temperature of' 150 C. to remove Water and themethanol. f

500 grams of this product were mixed with 37.4 grams of magnesiumchloride (MgClzHaO) and the mixture thus obtained was heated to atemperature of about 175 C. to remove residual methanol and water. Theresulting product was so viscous that it was found necessary to diluteit with 500 milliliters of mineral oil. The mixture was then filteredthrough clay. This product was found to contain 0.39% magnesium and0.81% sulfur indicating it to be mainly the neutral magnesium salt.

The oil-soluble, phosphorusand sulfur-containing reaction productscontemplated herein are those obtained by reacting a dicyclic terpeneand a phosphorus sulde at a temperature above about C. Although any oneof the several phosphorus sulfides such as PaSe (or PS2), P4Sn (0r P2S3)P483, P2Ss (0r P4810), P4S'l, etc., may be used in the preparation ofthe said reaction products, particularly preferred are those reactionproducts obtained using PaSs.

Dicyclic terpenes are defined herein as those terpenes which arecharacterized by the presence of one double bond in the molecule andwhich are comprised of two ring systems. Typical of such terpenes arepinene, camphene and fenchene.

contemplated as coming within this particular designation are thosematerials which are predominantly comprised of one or more dicyclicterpenes; representative of such materials are the essential or volatileoils which are predominantly comprised of such a terpene, or terpenes,and are typified by turpentine oil, the predominant constituent of whichis pinene. Preferred of the dicyclic terpene reactants are pinene andturpentine oil. Accordingly, the preferred reaction products are thoseobtained from Piss and pinene, and P255 and turpentine oil.

Although a, .complete understanding of the chemical composition of thereaction products contemplated here is not known at this time, a partialunderstanding of their composition may be realized by noting thecharacteristics involved in the reaction. The reaction betweenphosphorus pentasulde and pinene, for example, commences at about 100 C.and is exothermic in nature. During the reaction, the reaction mixtureincreases appreciably in viscosity and little, if any, hydrogen sulde isevolved therefrom. The reaction product obtained in this reactioncontains phosphorus and sulfur in substantially the same amounts as areadded through the particular phosphorus suliide used. It would appear,then, that the reaction is one of addition, that is, addition of theprosphorus suliide to the oneV unsaturated bond present in pinene.

While the reaction temperature for the reaction described above shouldbe one of at least about 100 C., the preferred temperatures fall withinthe range of about 100 C. to about 160 C.

The proportions of reactants used herein may be varied in order toprepare reaction products having different degrees of oil solubility anddifferent degrees of oil-improving power. It is preferred, however, touse about 1 mol of a phosphorus sulfide With 4 mols of a dicyclicterpene for the preparation of a reaction product readily soluble inpetroleum oils. For example, when more than 1 mol of PzSs is used with 4mols of pinene, a viscous gel-like reaction product is obtained Which isdifliculty soluble in petroleum oils. Also, when less than 1 mol of Passis used with 4 mols of pinene, a viscous oil somewhat insoluble inmineral oils is obtained after the unreacted pinene has been recoveredby distillation.

Accordingly, it is to -be understood that while effective mineral oilimproving. agents of the type contemplated herein can be obtained byusing different ratios of reactants, particularly preferred improvingagents are those obtained by using approximately 1 mol of a phosphorussulde for every 4 mols of a dicyclic terpene.

There is, however, still another desirable procedure for preparing thereaction products contemplated here. In order to obtain a relativelynon-viscous reaction product, a blend of a dicyclic terpene, such aspinene, and a comparatively inert solvent such as a petroleum oil, may

be treated as described above to provide an oil blend of the reactionproduct. The preferred procedure of this type involves the use of a 1:1

blend of dicyclic terpene and petroleum oil with a phosphorus sulfide,the molar ratio of said terpene to said sulde being 4:1.

Further details regarding the character of the aforesaid dicyclioterpene-phosphorus sulfide reaction products may be obtained byreferring to copending application Serial Number 482,482, filed April 9,1943, of Everett W. Fuller et al.

The following example illustrates these oilsoluble, phosphorusandsulfur-containing reaction products and the preparation thereof:

Examen: 3

After partial cooling of the mixture and the subsequent addition of 32grams of clay thereto, the mixture was iiltered. The filtrate whichweighed 1842 grams was subjected to distillation at a temperature of 150C. at 5 millimeters pressure. 149

grams of a low-boiling liquid were thus removed. The remaining productwas a clear, viscous oil containing 12.5% sulfur and 5.11% phosphorus,by weight.

The oil compositions contemplated herein may also contain, in additionto an oil detergent and a dicyclic terpene-phosphorus sulfide reactionproduct, a small amount of one or more other oil-soluble, phosphorusandsulfur-containing reaction products. One such reaction product is thatwhich is obtained by reaction of approximately one mol of phosphoruspentasulde with four mols of oleyl alcohol, or ocenol, at a temperaturefalling Within the range varying between about 125 C. and about 150 C.,for a relatively short time. These reaction lproducts are described infurther detail in copending application Serial Number 524,490, iledFebruary 29, 1944, now U. S. Patent No. 2,411,153, issued November 19,1946, of Everett W. Fuller et al. Another such reaction product is thatwhich'is obtained by reacting a cycle stock with about 5-15% by weightof phosphorus pentasuliide.v

This type of product is fully described in copending application SerialNumber 515,418, led December 23, 1943, now U. S. Patent No. 2,450,405,issued October 5, 1948 of Berger et al.

The following test results are provided to demonstrate the properties ofmineral oils containing small amounts of metal sulfonates, other .thanmagnesium sulfonates, oil detergents and of the aforementioned dicyclicterpene-phosphorus sulde reaction products, and "the outstandinglysuperior properties of mineral oils containing small amounts of themagnesium sulfonate oil detergents and of the aforementioned dicyclicterpene-phosphorus suliide reactionV products. The metal sulfonates,other than magnesium sulfonates, were prepared by reacting thediwaxphenyl sulfonic acid obtained in accordance with the procedure setforth in Example 1, with the proper metal hydroxide or chloride inaccordance with the procedures outlined in Examples 1 and 2.

The following metal sulfonates were thus prepared:

The oil-soluble, phosphorusand sulfur-containing reaction productutilized in preparing the mineral oil blends used in obtaining the testre- 7 suits set forth hereinafter was prepared in accordance with theprocedure set forth in Ex-` ample 3.

In each run, a. single-cylinder, 4-cycle, gasoline Lauson engine wasoperated for 30 hours with an 5 .oil temperature of 225? F., a jackettemperature of 350 F., at a speed of about 1830 R. P. M., at

one-half throttle, and using a 13:1 fuel (100% the type referred tohereinbefore were tested in the engine separately. At the end of eachrun,

vthe piston of the engine was examined and rated for lacquer and sludgedeposits, an engine cleanliness (E. C.) of 100 indicating a perfectlyclean 8 from about 0.10% to about 3.0%; in general, however, about 1.0%will be satisfactory.

As indicated herinbefore, .the mineral oil compositions of thisinvention may also contain one or more other oil-soluble, phosphorusandsulfur-containing reaction products, such as those obtained from cyclestocks and Pass, and' oleyl alcohol and Pass, all as dened above. Oilsof excellent quality are obtained with from labout l 0.10% to about 3.0%of such s. reaction product,

incorporated with the aforesaid quantities of a magnesium-containing oildetergent Aand of a dicyclic terpene reaction product of the typedefined hereinbefore.

Mineral oil concentrates are also contemplated herein, such concentratescontaining substantially larger concentrations of amagnesium sulfonateoil detergent and of a dicyclic lterpenephosphorus sulfide reactionproduct, than those piston and lower ratings indicating increasingenumerated abQVe- That iS, TelatiVely large amounts of deposits. Thepertinent data of each run are tabulated in Table II.

amounts of the said materials may be incorporated in an oil fraction inwhich they are readily Table II Per Cent oi Metal Example Metal Diwaxphenyl Pefty in o cllismm No. Sulfonate (Detergent) Detergent E` CRating Weight Mole 3. 0 0. 0387 0. 00160 89 l. 0 0. 0129 0. 00054 87 0.5 0. 0065 0. 00027 86 4. 0 0. 20 0. 00146 74 2.0 0. 10 0. 00073 76 1.00. 05 0. 00037 75 0. 5 0. 025 0. 00018 69 2. 5 0. 0115 0. 00047 63 f 4.0 0. 0156 0. 00065 87 do 2. 0 0.0078 0.00032 78 Neutral Ba... 5. 0 0.108 0. 00079 7l do 1.0 0.022 0.00016 68 Neutral Ca... 3.0 0.039 0.0009882 .do 1.5 0.0195 0.00049 76 Neutral Zn.-. 3.0 0. 0504 0. 00078 83 .do1.5 0.0252 0.00039 73 The relationships between the data set forth inTable 1I are presented graphically in Figures soluble, and the oilconcentrate so obtained may thereafter be diluted with a suitablequantity of 1 and 2, 45 the said oil fraction prior to use. It is to beIt will be apparent from inspection of the data tabulated in Table II,that the reference oil is comparatively unsatisfactory in view of itsrelatively low E. C. rating. It will be apparent also understood thatthese mineral oil concentrates may also contain one or more of theaforesaid other oil-soluble, phosphorusand sulfur-containing reactionproducts, such as those obtained that on a per cent by weight basis ofcomparison, from oleyl alcohol or a cycle stock, in .amounts themagnesium-containing detergents are superior to the other metalsuli'onates. This superiority is particularly marked in the case of thebasic magnesium sulfonates. When the comparisubstantially in excess ofthose described above.

In preparing the mineral oil compositions and concentrates contemplatedherein, an oil-soluble magnesium sulfonate and a dicyclic terpeneson ismade on the basis 0f per cent of metal in 55 phosphorus sulde reactionproduct, as defined hereinbefore, may be incorporated in a mineral oilin any one of several ways. For example, the

dicyclic terpene reaction product; may be added to an oil fractioncontaining .an oil-soluble magnesium sulfonate; also .an oil-solublemagnesium sulfonate may be added to the reactants (dicyclic terpene andphosphorus sulde) used in the preparation of the said reaction productand, in such case, will be present during the reaction.

high degree of resistance to oxidation and partic- It 1S possible thatthe oil-soluble magnesium sulularly desirable detergent properties.

As contemplated by the present invention, concentrations of from about0.5 per cent to about 10 per cent of a magnesium-containing oil defonatemay react with the dicyclic terpene and phosphorus sulde to form acomplex reaction product under the reaction conditions enumeratedherein; the product obtained in this manner tergent are used in an oilfraction, but coi'icen-` 70 may then be added to an oil fraction.Accordtrations of the order of about 2% have been found to,besatisfactory for most purposes. The concentration of the oil soluble,phosphorusand sulfur-containing reaction product of a dlcyclic ingly; itwill be apparent that the mineral oil compositions and concentrates ofthis invention 1 are complex in nature, for it is posisble that anoil-soluble magnesium sulfonate and a dicyclic terpene and a phosphorussulde may be varied 75 terpene-phosphorus sulfide reaction product may l9 be present individually in an oil fraction, or may also be presenttherein as a physical combination or, further, may be present therein inthe form of a single chemical composition. In the same connection, itwill also be apparent that an oil-soluble magnesium sulfonate and areaction product of the aforesaid type may enter into chemical reactionwhen the oil composition is used as a lubricant under certainconditions, such forexample, as a lubricant in an engine operating atrelatively high temperatures.

In view of the foregoing,l the term "mineral oil composition, as usedherein, and as recited in all of the appended claims, isinclusive of allmineral oil fractions containing an oil-soluble magnesium sulfonate and'a dicycllc terpenephosphorus sulfide reaction product of the typedeilned hereinbefore, in the concentrations previously enumerated, andis inclusive of oil compositions obtained or prepared by any of theaforesaid several procedures. Correspondingly, the term "mineral oilconcentrate is inclusive o! all mineral oil fractions containingrelatively large amounts of the said oil-soluble magnesium sulfonatesand said reaction product.

It is to be understood that the examples, procedures and oilcompositionsk describedrhereinbefore are illustrative only and are notto be construed as limiting the scope of this invention thereto. Forexample, all dicycllc terpenes as broadly recited herein may be used inplace of pinene shown in the examples; however, pinene is preferred.Similarly, any phosphorus sulde may be used in place of phosphoruspente-sulfide shown in the examples, but the latter phosphorus sulildeis preferred. Also, while the magnesium diwax phenyl sulfonates arepreferred, al1 other oil-soluble magnesium sulfonates coming within thedeiinition herein of a magnesium-containing oil-detergent may be used.Furthermore, the mineral oil fraction disclosed herein is but typical ofthe mineral oil fractions which may be used.

-We claim:

1. An improved mineral oil composition comprising a viscous mineral oilfraction having in admixture therewith a minor proportion, from about0.5 per cent to about 5.0 per cent, of an oil-soluble magnesiumsulfonate; and a minor proportion, from about 0.10 per cent 'to about3.0 per cent, of an oil-soluble. phosphorusand sulfur-containingreaction product obtained by reaction of substantially one mol of aphosphorus sulfide with four mols of a material selected from the groupconsisting of a dicyclic terpene and an essential oil predominantlyconsisting of a dicycllc terpene, at a temperature varying between about100" C. and about 160 C.

2. An improved mineral oil composition comprising a. viscous mineral oilfraction having in admixture therewith a minor proportion, from about0.5 per cent to about 5.0 per cent, of an oilsoluble magnesiumsulfonate;` and a minor proportion, from about 0.10 per cent to about3.0 per cent, of an oil-soluble, phosphorusand sulfurcontaining reactionproduct obtained by reaction of substantially one mol of phosphoruspentasulde and four mols of a material selected from the groupconsisting of a dicyclic terpene and an essential oil predominantlyconsisting of a dicycllc terpene, at a temperature varying between about100 C. and about 160 C.

3. An improved mineral oil composition comprising a viscous mineral oilfraction having in admixture therewith a minor proportion, from about0.5 per cent toabout 5.0 per cent, of an oilsoluble magnesium salt of awax-substituted aromatic sulfonic acid; and a minor proportion, fromabout 0.10 per cent to about 3.0 per cent, of an oil-soluble,phosphorusand sulfur-containing reaction product obtained` by reactionof substantially one mol of a phosphorus sulfide with four mols of amaterial V`selected from the group consisting of a dicycllc terpene andan essential oil predominantly consisting of a dicycllc terpene, at atemperature varying between about 100 C. and about 160 C.

4. An improved mineral oil composition comprising a viscous mineral oilfraction having in admixture therewith a minor proportion, from about0.5 per cent to about 5.0 per cent, of an oilsoluble magnesium salt of awax-substituted aromatic sulfonic acid; and a minor proportion, fromabout 0.10 per cent to about 3.0 per cent, of an oil-soluble,phosphorusand sulfur-containing reaction product obtained by reaction ofsubstan- 1 tially one mol of phosphorus pentasulde and Cil four mols ofa material selected from the group consisting of a dicycllc terpene andan essential oil predominantly consisting of a dicyclic ter-4 solublemagnesium salt of a wax-substituted benzene sulfonic acid; and a minorproportion, from about 0.10 per cent to about 3.0 per cent, of anoilsoluble, phosphorusand sulfur-containing reaction product obtained byreaction o1' substantially one mol of a phosphorus sulilde with fourmols of a material selected from the group consisting of a dicyclicterpene and an essential oil predominantly consisting or a dicylicterpene, at a ternpgature varying between about C. and about l C.

6. An improved mineral oil composition comprising a viscous mineral ,oilfraction having in admixture` therewith a minor proportion, from about0.5 per cent to about 5.0 per cent, of an oilsoluble magnesium salt ofa. wax-substituted benzene sulfonic acid; and a minor proportion, fromabout 0.10 per cent to about 3.0 per cent, of an oilsoluble,phosphorusand sulfur-containing reaction product obtained by reaction ofsubstantially one mol of phosphorus pentasulfide and four mols of amaterial selected from the group consisting of a dicycllc terpene and anessential oil predominantly consisting of a dicycllc terpene. at atemperature varying between about 100 C. and about C.

7. An improved mineral oil composition comprising a viscous mineral oilfraction having in admixture therewith a minor proportion, from about,0.5 per v'cient-.15b about 5.0 per cent, of an oil-soluble magnesiumsalt of a diwax-substituted benzene sulforiic acid; and a minorproportion, from about 0.10 per cent to about 3.0 percent, of anoil-soluble, phosphorusand sulfur-containing reaction product obtainedby reaction of substantially one mol of a phosphorus sulfide with fourmols of a material selected from the group consisting of a dicyclicterpene and an essential oil predominantly consisting of a dicycllcterpene, at a temperature varying between about 100 C. and about 160 C.

8. An improved mineral oil composition comprising a viscous mineral oilfraction having in admixture therewith a minor proportion, from about0.5 per cent to about 5.0 per cent, of an oil- 11 soluble magnesium saltof a diwax-substituted benzene sulfonic acid; and a minor proportion,from about 0.10 per cent to about 3.0 per cent, of an oil-soluble,phosphorusand sulfur-containing reaction product obtained by reaction ofsubstantially one mol of phosphorus pentasulde and four mols of amaterial selected from the group consisting of a dicyclic terpene and anessential oil predominantly consisting of a dfcylic terpene.:

at a temperature varying between about 100 C. and about 160 C. V A

9. An improved.- mineral oil composition comprising a. viscous mineraloll fraction having in admixture therewith a minor proportion, from` 10.An improved mineral oil composition comprising a viscous mineral oiltraction having in admixture therewith va minor proportion, from about0.5 per cent to about 5.0 per cent, of an oil-soluble basic magnesiumsalt of a diwaxsubstituted benzene sulfonlc acid; and a minorproportion, from about 0.10 per cent to about 3.0 per cent, of anoil-soluble, phosphorusand sulfur-containing reaction product obtainedlby reaction of substantially one mol of phosphorus pentasultlde andfour mols of a material selected from the group consisting of a dicylicterpene and an essential oil predominantly consisting of a dicyclicterpene, at a temperature varying between about 100 C. and about 160 C.

EVERETT. W. FULLER. ELLWOOD M. JOHNSON.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,379,453 Noland July 3, 19452,402,325 Grlesinger June 18, 1946 2,416,281 Berger Feb. 25, 1947

